CN116715967B - Glyphosate molecularly imprinted polymer based on virtual template and application thereof - Google Patents
Glyphosate molecularly imprinted polymer based on virtual template and application thereof Download PDFInfo
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 105
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 105
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 16
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 15
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical class NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 17
- 239000002207 metabolite Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 9
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- 239000012086 standard solution Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
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- 238000004140 cleaning Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000000575 pesticide Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- NEOGGGHDLGYATP-UHFFFAOYSA-N 1,6-dimethylimidazo[4,5-b]pyridin-2-amine Chemical compound CC1=CN=C2N=C(N)N(C)C2=C1 NEOGGGHDLGYATP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000027455 binding Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- IAANMKMHMYZVOC-UHFFFAOYSA-N aminomethyl dihydrogen phosphate Chemical compound NCOP(O)(O)=O IAANMKMHMYZVOC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 230000009870 specific binding Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- XBJFCYDKBDVADW-UHFFFAOYSA-N acetonitrile;formic acid Chemical compound CC#N.OC=O XBJFCYDKBDVADW-UHFFFAOYSA-N 0.000 description 1
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- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 1
- 229950001327 dichlorvos Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
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- WYMSBXTXOHUIGT-UHFFFAOYSA-N paraoxon Chemical compound CCOP(=O)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 WYMSBXTXOHUIGT-UHFFFAOYSA-N 0.000 description 1
- 229960004623 paraoxon Drugs 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
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- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
- B01D15/3852—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36 using imprinted phases or molecular recognition; using imprinted phases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of molecular imprinting, in particular to a glyphosate molecular imprinting polymer based on a virtual template and application thereof. The glyphosate virtual template molecularly imprinted polymer is prepared by using glyphosate as template molecules, 3-aminopropyl triethoxysilane as a functional monomer, tetraethoxysilane as a cross-linking agent, ammonia water as a catalyst and a sol-gel method; wherein the dosage ratio of the glyphosate to the 3-aminopropyl triethoxysilane to the ethyl orthosilicate is 1:4-8:8-16. According to the invention, gan Lin is taken as a virtual template molecule, a sol-gel method is adopted to prepare a molecularly imprinted polymer, and the molecularly imprinted polymer can be used for carrying out specific adsorption on glyphosate and an amino methyl phosphonic acid metabolite thereof simultaneously, and detecting the glyphosate and the amino methyl phosphonic acid metabolite thereof simultaneously.
Description
Technical Field
The invention relates to the technical field of molecular imprinting, in particular to a glyphosate molecular imprinting polymer based on a virtual template and application thereof.
Background
The pretreatment process of the complex matrix is a key step of pesticide analysis and detection. The solid phase extraction and its derivative technology can separate and pre-enrich target analyte from real sample, and has the advantages of high efficiency, easy separation and saving solvent, but lack of specificity. Various enzyme/antibody-based methods have also been used to achieve specific recognition of target substances, however, their poor chemical/physical stability limits their use in alkaline or acid, organic solvents and harsh environments at high temperatures. The molecular imprinting technology (Molecular imprinting technology, MIT) is used for improving the recognition selectivity and the detection sensitivity due to low cost, specific recognition, simple preparation and good thermal stability, and is widely applied to various fields.
MIPs are artificially generated synthetic polymeric materials with recognition sites that mimic the specific binding principle of enzymes to substrates or antigens to antibodies, enabling specific recognition, enrichment and isolation of target molecules. The functional groups and the arrangement of functional groups of the binding sites within the cavity can influence the recognition capability of the MIP, and are synthesized mainly by covalent, semi-covalent or non-covalent methods. Under the crosslinking action of the crosslinking agent, a polymer is formed between the template molecule and the functional monomer. Upon removal of the template, binding sites for specific cavities complementary in shape, size and functionality to the target molecule are generated.
The molecular imprinting solid phase extraction has the characteristics of strong specificity, good separation effect and the like, and can effectively remove the interference of sample matrixes and certain impurities on detection results. However, in the synthesis process of the conventional molecularly imprinted polymer, a part of template molecules often remain, leak out of the molecularly imprinted polymer, possibly interfere with detection results and generate false positive results. Therefore, some scholars begin to use structural analogues of target molecules as template molecules in the synthesis of molecularly imprinted polymers to avoid the influence of leakage of the template molecules. At present, although some researches on the preparation of glyphosate virtual template molecularly imprinted polymers are reported, no report on the synthesis of glyphosate molecularly imprinted polymers by using a virtual template is seen.
Glyphosate is a widely used herbicide, and glyphosate and its main metabolite amino methyl phosphonic acid remain in the environment and plants, which can cause environmental damage and threaten human health. Thus, there is a need to establish a method for simultaneous detection of glyphosate and its metabolite amino methyl phosphonic acid.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a glyphosate molecularly imprinted polymer based on a virtual template and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in the first aspect, a glyphosate molecularly imprinted polymer based on a virtual template is provided, which is prepared by using glyphosate as a template molecule, 3-aminopropyl triethoxysilane as a functional monomer, ethyl orthosilicate as a cross-linking agent, ammonia water as a catalyst and a sol-gel method; wherein the dosage ratio of the glyphosate to the 3-aminopropyl triethoxysilane to the ethyl orthosilicate is 1:4-8:8-16.
Further, the dosage ratio of the glyphosate, the 3-aminopropyl triethoxysilane and the tetraethoxysilane is 1:6:12.
in a second aspect, a preparation method of a glyphosate molecularly imprinted polymer based on a virtual template is provided, and the preparation method comprises the following steps:
adding functional monomer 3-aminopropyl triethoxy silane, cross-linking agent tetraethoxysilane and catalyst ammonia water to react after dissolving the glyphosate serving as a template molecule, wherein the dosage ratio of the glyphosate to the 3-aminopropyl triethoxy silane to the tetraethoxysilane is 1:6:12; and after the reaction is finished, aging, centrifuging, washing and drying to obtain the white powder solid glyphosate virtual template molecularly imprinted polymer.
In a third aspect, an application of a glyphosate virtual template molecularly imprinted polymer in simultaneous detection of glyphosate and its metabolite amino methyl phosphonic acid is provided.
Further, glyphosate and its metabolite amino methyl phosphonic acid are detected simultaneously by preparing a glyphosate molecularly imprinted solid phase extraction column.
Further, the preparation method of the glyphosate molecular imprinting solid phase extraction column comprises the following steps:
step 1, a sieve plate with the aperture of 20 mu m is arranged at the bottom of a 3mL solid phase extraction column;
step 2, weighing 50mg of glyphosate virtual template molecularly imprinted polymer by adopting a dry column packing mode, and filling the glyphosate virtual template molecularly imprinted polymer into a solid-phase extraction column;
and 3, attaching a filler on the top of the solid phase extraction column by using a sieve plate, activating the extraction column by using 3mL of methanol and water, adding 1mL of glyphosate standard solution with the concentration of 5mg/kg, and cleaning impurities by using 2mL of methanol and 2mL of water as eluent.
Further, ammonia water is used as eluent, and the concentration of the ammonia water is less than or equal to 0.1mM.
In a fourth aspect, an application of a glyphosate virtual template molecularly imprinted polymer in determining glyphosate selective adsorption is provided.
The beneficial effects of the invention are as follows:
according to the invention, gan Lin is taken as a virtual template molecule, and a sol-gel method is adopted to prepare the molecularly imprinted polymer, so that the glyphosate and the metabolite amino methyl phosphonic acid thereof can be subjected to specific adsorption at the same time, and a method for simultaneously detecting the glyphosate and the metabolite thereof is established.
Drawings
FIG. 1 is a diagram showing the chemical structural formulas of glyphosate and Zeng Gan Linhua in example 1 of the present invention;
FIG. 2 is a schematic diagram of the synthetic route of the glyphosate virtual template molecularly imprinted polymer of example 1 of the present invention;
FIG. 3 is a schematic representation of isothermal adsorption of glyphosate by increased Gan Lin-DMIP in example 2 of the present invention;
FIG. 4 is a graph showing the result of optimizing the concentration of the eluent in example 3 of the present invention;
FIG. 5 is a graph showing the recovery results of various pesticides in example 4 of the present invention; wherein the left side represents MIP and the right side represents NIP;
FIG. 6 is a linear graph of liquid chromatography tandem mass spectrometry detection of glyphosate in example 4 of the present invention;
FIG. 7 is a linear graph of the detection of aminomethylphosphonic acid by liquid chromatography tandem mass spectrometry in example 4 of the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate understanding of the present invention by those skilled in the art, but it should be understood that the present invention is not limited to the scope of the embodiments, and all the inventions which make use of the inventive concept are protected by the spirit and scope of the present invention as defined and defined in the appended claims to those skilled in the art.
Example 1 preparation of glyphosate virtual template molecularly imprinted Polymer
Referring to fig. 1-2, glyphosate, a structural analog of glyphosate, was selected as a virtual template molecule, and a sol-gel method was used to synthesize glyphosate virtual template molecularly imprinted polymers (Dummy Molecularly Imprinted Polymers, DMIPs).
Specifically, 1mmol (271.2 mg) of glyphosate was weighed and dissolved in 30mL of ultrapure water, after 10 minutes of ultrasonic treatment, 1432. Mu.L of 3-aminopropyl triethoxysilane (APTES), a functional monomer, was added, and ultrasonic treatment was carried out for 30 minutes. Then 2676 μl of cross-linking agent tetraethyl orthosilicate (Tetraethyl Orthosilicate, TEOS) was added and sonicated for 30min. Finally, 100 mu L of catalyst ammonia water is added, and the mixture is placed in a water bath kettle at 60 ℃ for magnetic stirring for 12 hours. After the reaction, the mixture was put into a water bath shaker and aged for 3 hours at room temperature, and centrifuged for 8 minutes in a centrifuge with a rotation speed of 5000 rpm. 30mL of methanol was used first: the solution is washed three times by shaking acetic acid (9:1), and then washed by 1mM hydrochloric acid, so that the molecular engram polymer is prevented from gelation. And washing the product twice by using ethanol, and drying the product in a vacuum drying oven at 60 ℃ to obtain the white powder solid glyphosate virtual template molecularly imprinted polymer.
In this example, glyphosate has very similar physical/chemical properties to its structural analog, glyphosate, is insoluble in organic solvents, and has a strong polarity. The sol-gel method is suitable for preparing the molecular imprinting material by using the water-soluble compound, and uses the glyphosate as a template molecule, so that the preparation cost is reduced, and false positive results are prevented. In the preparation process of the present example, the ratios of template molecule, solvent, functional monomer and crosslinking agent were optimized, and table 1 is the designed optimization conditions. The catalytic conditions are optimized, and two catalysts of ammonia water and hydrochloric acid are screened. The system using HCl as catalyst has no molecular engram polymer generation or trace generation, and the reaction is incomplete, so that NH is determined 3 ·H 2 O is used as a catalytic system. Changing the volume of porogen added, adding a small volume of porogen resulted in a small amount of yellow material eluting out from the bottom of the round bottom flask, which may be an increase Gan Lin that did not fully participate in the polymerization reaction. The proper amount of cross-linking agent increases the stability and binding capacity of the polymer, optimizes several proportions of cross-linking agent, and compares the adsorption performance of the synthesized polymer through the adsorption quantity. When the ratio of the glyphosate to APTES to TEOS is 1:6: at 5, the adsorption amount of the imprinted polymer was 820. Mu.g/g. Ratio of whenExample is lifted to 1:6: at 12, the adsorption amount was 1619. Mu.g/g in this case, which is the optimal polymerization system.
TABLE 1 optimization of DMIPs polymerization conditions
EXAMPLE 2 evaluation of adsorption Performance of glyphosate virtual template molecularly imprinted Polymer
(1) Dynamic adsorption
5mg of DMIPs and DNIPs (blank) are weighed respectively, placed in a 2mL centrifuge tube, 1mL of glyphosate solution with the concentration of 20mg/kg is placed in the centrifuge tube, and is oscillated in a shaking table at the oscillation speed of 200rpm at room temperature, and sampling is carried out according to a certain time, namely 1min, 3min, 5min, 10min, 20min, 30min, 40min and 60min respectively. Then centrifuging at 6000rpm for 5min, collecting supernatant, filtering with 0.22 μm filter membrane, and detecting the filtrate in a machine. And (3) calculating the adsorption quantity Q of the glyphosate molecules DMIPs and DNIPs to the glyphosate according to a formula 3-1, and drawing a dynamic adsorption curve according to the adsorption quantity Q.
Wherein: adsorption amount of glyphosate (μg/mg) by the imprinted polymer at Q balance
C 0 Initial concentration of glyphosate (mg/L)
C m Adsorption equilibrium supernatant glyphosate concentration (mg/L)
V adding the volume of glyphosate solution (L)
Addition amount of m-imprinted Polymer (mg)
(2) Static adsorption
According to the optimal adsorption saturation time determined by dynamic adsorption, 1mg L of the catalyst is configured -1 ,5mg L -1 ,10mg L -1 ,20mg L -1 ,50mg L -1 ,80mg L -1 ,100mg L -1 ,160mg L -1 ,200mg L -1 ,500mg L -1 Standard solutions of glyphosate at various concentrations were taken 1mL and placed in a solution containing 5mg of DMIPs and DNIPsCentrifuging in a centrifuge tube, taking a supernatant filtering membrane, and detecting the content of glyphosate in filtrate by using LC/MS/MS. Calculating Q according to the formula max And K d The adsorption amount calculation formula is shown as 3-2:
wherein: adsorption capacity (mug/g) of glyphosate by imprinted polymer at Q balance
C m Adsorption equilibrium supernatant glyphosate concentration (μg/mL)
Q max Maximum apparent adsorption quantity (μg/mg)
K d Binding constant
In this example, the adsorption difference between DMIP and DNIP at different concentrations of glyphosate standard solution was investigated based on the saturation adsorption time (30 min) determined by the DMIP adsorption kinetics curve. The isothermal adsorption curve is shown in FIG. 3, in the extremely low concentration range (1-4 mg/L), the adsorption amount of DMIP and DNIP does not have significant difference change, and the adsorption of DMIP to glyphosate may be mainly nonspecific adsorption; when the concentration is higher than 10mg/L, the difference is gradually obvious, and the adsorption capacity is linearly increased along with the change of the concentration of the glyphosate. At the same time, the adsorption capacity increases far more than DNIP, presumably the variability caused by specific binding sites; however, when the concentration of glyphosate reached 200mg/L, the adsorption curve became gentle, indicating that the maximum adsorption capacity was reached at this time. In conclusion, the DMIP material has specific adsorption capacity to glyphosate.
Example 3 preparation of glyphosate molecularly imprinted solid phase extraction column
A virtual template molecularly imprinted solid phase Extraction (DMI-SPE) column is prepared, and a sieve plate with the aperture of 20 μm is firstly filled into the bottom of a 3mL solid phase Extraction column with the assistance of a glass rod. And (3) filling 50mg of Gan Lin-DMIPs into the solid phase extraction column by adopting a dry column filling mode. And finally, a piece of sieve plate is used for attaching a filler on the top of the sieve tube, so that the filler cannot be compacted too tightly or too loosely, and the adsorption capacity and the mass transfer efficiency can be influenced. 3mL of methanol and water were used to activate the extraction column, 1mL of glyphosate standard solution at a concentration of 5mg/kg was added, and 2mL of methanol and 2mL of water were used as a eluent to clean the impurities.
In this example, because of the acidic nature of glyphosate, common organic solvents and water are not able to elute adsorbed glyphosate. When ammonia water is used as eluent, the eluting effect of the glyphosate is better, so that the concentration of the ammonia water in the eluent is optimized. From fig. 4, it can be seen that the glyphosate recovery rate tends to increase as the concentration of aqueous ammonia increases. After exceeding 0.1mM, the recovery rate starts to decrease.
Example 4 evaluation of glyphosate DMI-SPE column specificity
Parathion, paraoxon, dichlorvos and trichlorfon are pesticides commonly detected in wheat, so these four pesticides were selected in this example for further evaluation of the specificity of the enriched Gan Lin DMI-SPE column. The structural formulas of the four organophosphorus pesticides have great differences compared with the chemical structure of the glyphosate. The four pesticides were passed through a DMI-SPE column, the eluent was detected using LC-MS/MS and the recovery was calculated, and the specificity of the DMI-SPE column was verified by the recovery results. The recovery results of the four pesticides are shown in figure 5, which shows that the DMI-SPE column has no specificity for drugs with great structural variability. Meanwhile, the specificity of the DMI-SPE molecular imprinting solid phase extraction column is researched by using glyphosate and a metabolite aminomethyl phosphoric acid thereof, and the recovery rates of the glyphosate and the metabolic aminomethyl phosphonic acid thereof are respectively 98% and 108%. The glyphosate DMI-SPE column can be used for specifically adsorbing glyphosate and a metabolite aminomethyl phosphoric acid thereof.
In this example, the glyphosate liquid chromatography tandem mass spectrometry was established as follows:
(1) Chromatographic conditions
LC-MS/MS analysis was tested using LCMS-8060 triple quadrupole mass spectrometer (shimadzu, japan). Chromatographic column: anionic Polar pesticide column temperature (5 mm, 2.1X100 mm): sample injection amount at 40 ℃): 2. Mu.L.
Mobile phase a:0.9% formic acid aqueous mobile phase B:0.9% acetonitrile formate; pump mode: binary high pressure gradients; total flow rate: 0.4mL/min. The time program is shown in table 2.
TABLE 2 time program
(2) Mass spectrometry conditions
Ion source: ESI, negative ion mode; capillary voltage: 4000V; the capillary temperature is 300 ℃; atomizer flow rate: 3.0L/min; type of collision gas: argon gas; scanning mode: monitoring multiple reactions; monitoring ions: see table 3.
TABLE 3 parent ion and ion parameter tables to be measured
Note that: the parent ion and ion parameters measured in the mass spectrum are the best conditions optimized by using the instrument.
In this example, the feasibility of a DMI-SPE column was verified using LC-MS/MS, blank wheat extract was formulated into glyphosate standard solutions of different concentrations, and a matrix standard curve was established. As shown in FIGS. 6-7, the linear range of glyphosate is 0.05-10 μg/mL, the correlation coefficient is 0.999, the detection Limit (LOD) is 0.03 μg/mL, and the quantification Limit (LOQ) is 0.3 μg/mL; the linear range of aminomethylphosphoric acid is 0.05to 4. Mu.g/mL, the correlation coefficient is 0.991, the detection Limit (LOD) is 0.15. Mu.g/mL, and the quantification Limit (LOQ) is 0.5. Mu.g/mL.
According to the invention, gan Lin is taken as a virtual template molecule, and a sol-gel method is adopted to prepare the molecularly imprinted polymer, so that the glyphosate and the metabolite amino methyl phosphonic acid thereof can be subjected to specific adsorption at the same time, and a method for simultaneously detecting the glyphosate and the metabolite thereof is established.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The glyphosate molecularly imprinted polymer based on the virtual template is characterized in that glyphosate is taken as a template molecule, 3-aminopropyl triethoxysilane is taken as a functional monomer, tetraethoxysilane is taken as a cross-linking agent, ammonia water is taken as a catalyst, and the glyphosate molecularly imprinted polymer is prepared by a sol-gel method; wherein the dosage ratio of the glyphosate to the 3-aminopropyl triethoxysilane to the ethyl orthosilicate is 1:4-8:8-16.
2. The virtual template-based glyphosate molecularly imprinted polymer of claim 1, wherein the dosage ratio of glyphosate, 3-aminopropyl triethoxysilane, and ethyl orthosilicate is 1:6:12.
3. the preparation method of the glyphosate molecularly imprinted polymer based on the virtual template is characterized by comprising the following steps:
adding functional monomer 3-aminopropyl triethoxy silane, cross-linking agent tetraethoxysilane and catalyst ammonia water to react after dissolving the glyphosate serving as a template molecule, wherein the dosage ratio of the glyphosate to the 3-aminopropyl triethoxy silane to the tetraethoxysilane is 1:6:12; and after the reaction is finished, aging, centrifuging, washing and drying to obtain the white powder solid glyphosate virtual template molecularly imprinted polymer.
4. The application of the glyphosate molecularly imprinted polymer based on the virtual template in the method of claim 1 or 2 or the glyphosate molecularly imprinted polymer based on the virtual template prepared by the method of claim 3 in the simultaneous detection of glyphosate and the metabolite amino methyl phosphonic acid thereof.
5. The use according to claim 4, wherein glyphosate and its metabolite amino methyl phosphonic acid are detected simultaneously by preparing a glyphosate molecularly imprinted solid phase extraction column.
6. The use according to claim 5, wherein the preparation method of the glyphosate molecularly imprinted solid phase extraction column comprises the following steps:
step 1, a sieve plate with the aperture of 20 mu m is arranged at the bottom of a 3mL solid phase extraction column;
step 2, weighing 50mg of glyphosate virtual template molecularly imprinted polymer by adopting a dry column packing mode, and filling the glyphosate virtual template molecularly imprinted polymer into a solid-phase extraction column;
and 3, attaching a filler on the top of the solid phase extraction column by using a sieve plate, activating the extraction column by using 3mL of methanol and water, adding 1mL of glyphosate standard solution with the concentration of 5mg/kg, and cleaning impurities by using 2mL of methanol and 2mL of water as eluent.
7. The use according to claim 5 or 6, characterized in that ammonia is used as eluent, the concentration of ammonia being less than or equal to 0.1mM.
8. The use of the virtual template-based glyphosate molecularly imprinted polymer of claim 1 or 2 or the virtual template-based glyphosate molecularly imprinted polymer prepared by the preparation method of claim 3 in determining glyphosate selective adsorption.
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| CN109001279A (en) * | 2018-07-25 | 2018-12-14 | 江南大学 | A kind of preparation and application of glyphosate molecular engram electrode |
| CN109092254A (en) * | 2018-08-16 | 2018-12-28 | 广东工业大学 | A kind of preparation of double virtual template phthalic acid ester molecular engram magnetic materials and application method |
| CN109776811A (en) * | 2017-11-15 | 2019-05-21 | 浙江工商大学 | A kind of preparation and application of glyphosate molecular imprinted solid phase extraction cartridge |
| WO2022122399A1 (en) * | 2020-12-07 | 2022-06-16 | Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie, Dieser Vertreten Durch Den Präsidenten Der Bundesanstalt Für Materialforschung Und -Prüfung, (Bam) | Molecularly imprinted fluorescent polymers for direct detection of glyphosate, its degradation products, and metabolites |
| CN115479929A (en) * | 2022-10-11 | 2022-12-16 | 南京师范大学 | Fluorescent test paper for detecting glyphosate, preparation method and application thereof |
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| CN109776811A (en) * | 2017-11-15 | 2019-05-21 | 浙江工商大学 | A kind of preparation and application of glyphosate molecular imprinted solid phase extraction cartridge |
| CN109001279A (en) * | 2018-07-25 | 2018-12-14 | 江南大学 | A kind of preparation and application of glyphosate molecular engram electrode |
| CN109092254A (en) * | 2018-08-16 | 2018-12-28 | 广东工业大学 | A kind of preparation of double virtual template phthalic acid ester molecular engram magnetic materials and application method |
| WO2022122399A1 (en) * | 2020-12-07 | 2022-06-16 | Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie, Dieser Vertreten Durch Den Präsidenten Der Bundesanstalt Für Materialforschung Und -Prüfung, (Bam) | Molecularly imprinted fluorescent polymers for direct detection of glyphosate, its degradation products, and metabolites |
| CN115479929A (en) * | 2022-10-11 | 2022-12-16 | 南京师范大学 | Fluorescent test paper for detecting glyphosate, preparation method and application thereof |
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